2-ethoxyazulene | 91962-49-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-ethoxyazulene
• CAS: 91962-49-1
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: WAVNIIACMSBMKI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-ethoxyazulene 在 tris-(dibenzylideneacetone)dipalladium(0) 、 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 、 双(2-二苯基磷苯基)醚 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  Toward Singlet–Triplet Bistable Nonalternant Kekulé Hydrocarbons: Azulene-to-Naphthalene Rearrangement

  摘要：

  Recent developments of open-shell singlet diradicaloids motivated the search for stable singlet-triplet bistable nonaltemant polycyclic hydrocarbons. During the synthesis of this type of molecule, such as the dibenzo-cyclohepta[def]fluorene 3, an unexpected azulene-to-naphthalene rearrangement was observed at room temperature, which resulted in new nonaltemant hydrocarbons 8a/8b with a closed-shell singlet ground state. These studies provided insight into the unique chemistry of azulene and challenges for the synthesis of singlet-triplet bistable polycyclic hydrocarbons.

  DOI：

  10.1021/acs.orglett.5b03028
• 作为产物：
  描述：

  ethyl 2-chloroazulene-1-carboxylate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 生成 2-ethoxyazulene
  参考文献：
  名称：

  Synthesis of 2-Substituted Azulenes by Nucleophilic Substitution Reactions of 2-Haloazulene Derivatives

  摘要：

  DOI：

  10.1246/bcsj.35.1990

文献信息

• The formation of azulene derivatives from 2H-cyclohepta[b]furan-2-one derivatives
  作者：T. Nozoe、K. Takase、T. Nakazawa、S. Fukuda

  DOI：10.1016/s0040-4020(01)97748-8

  日期：——

  ethoxide or t-butyl-amine, giving the corresponding 1,2,3-trisubstituted azulene derivatives, respectively. The structures of these azulene derivatives are determined on the basis of chemical evidence, and spectral data. Considering the structural correlation between the starting 2H-cyclohepta[b]furan-2-ones and the azulene derivatives obtained, a reasonable reaction course, involving the heptafulvene-type

  3-乙氧基羰基-和3-乙酰基-2 H-环庚[ b ]呋喃-2-酮易于与丙二腈反应。氰基乙酰胺，氰基乙酸乙酯和丙二酸二乙酯，在乙醇钠或叔丁胺的存在下，分别得到相应的1,2,3-三取代的z并衍生物。这些a菁衍生物的结构是根据化学证据和光谱数据确定的。考虑到起始的2 H-环庚[ b ]呋喃-2-酮与所获得的氮杂环戊烯衍生物之间的结构相关性，提出了一种合理的反应过程，涉及七富烯型和二氢氮杂环戊烷型中间体，可用于从中形成氮杂环戊烯衍生物。 2 H-环庚基[ b]呋喃-2-酮。
• On the reaction of prop-2-enylidenetriphenylphosphorane derivatives. Novel synthesis of the azulene ring system
  作者：Tohru Takayasu、Makoto Nitta

  DOI：10.1039/a605581h

  日期：——

  Reaction of prop-2-enylidenetriphenylphosphorane derivatives with several tropones has been studied in an attempt to provide a short new route to the azulene ring system. (2-Ethoxyprop-2-enylidene)triphenylphosphorane 4 reacts with 2-chloro-, 2-methoxy- and 2,3,5,7-tetrachlorotropones 7a–c to give azulene derivatives 8 and 9 in moderate yields. On the other hand, reaction of [2-ethoxy-3-(ethoxycarbonyl)prop-2-enylidene]triphenylphosphorane 6 with tropones 7a,c results in the formation of azulene esters 10 and 11 in low yields, whilst that with tropone 7b gives no azulene and substrate 7b is recovered. In order to gain insight into the mechanistic pathways, reaction of phosphoranes 4 and 6 with deuteriated tropones 14a,b which are the corresponding trideuteriated derivatives of compounds 7a,b, have also been studied. Furthermore, compound 4 reacts also with 5-(dimethylaminomethylene)cyclopenta-1,3-dienecarbaldehyde 33 to give 6-ethoxyazulene 37 in moderate yield.

  丙-2-烯基三苯基正膦衍生物与 对几种托酮进行了研究，试图提供一个简短的新方法 通向甘菊环系统的路线。 (2-乙氧基丙-2-亚乙烯基)三苯基正膦 4 与 2-氯-, 2-甲氧基- 和 2,3,5,7-四氯托酮 7a–c 得到甘菊环 衍生物8和9的产率适中。另一方面，反应 [2-乙氧基-3-(乙氧基羰基)丙-2-亚乙烯基]三苯基正膦 6 与 托酮 7a,c 导致形成甘菊酯 10 和 11 产率低，而使用托品酮 7b 则不产生甘菊环和底物 7b被恢复。为了深入了解机制途径， 正膦 4 和 6 与氘化托酮 14a,b 的反应 是化合物 7a,b 相应的三氘代衍生物，有 也被研究过。此外，化合物4还与 5-(二甲基氨基亚甲基)环戊-1,3-二烯甲醛 33 得到 6-乙氧基甘菊环37，产率中等。
• On the reaction of prop-2-enylidenetriphenylphosphorane derivatives. Novel synthesis of 4,9-methanocyclopentacycloundecene derivatives and their spectroscopic and chemical properties
  作者：Tohru Takayasu、Makoto Nitta

  DOI：10.1039/a703314a

  日期：——

  Novel 3-ethoxycarbonyl-2-ethoxy- and 2-ethoxy-4,9-methanocyclopentacycloundecenes 12 and 13 are synthesized by the reaction of 9-chloro-1,6-methano[11]annulen-8-one 8, a 10π-electron vinylogue of 2-chlorotropone, with 2-ethoxy-3-(ethoxycarbonyl)prop-2-enylidene- and 2-ethoxyprop-2-enylidenetriphenylphosphorane, 7a and 7b, respectively. The reaction pathways involve a Michael-type addition of phosphoranes 7a,b onto ketone 8, subsequent proton migration regenerating the phosphorane moiety, which undergoes intramolecular Wittig reaction, and aromatization, eliminating HCl. The 1H NMR spectra show that compounds 12 and 13 are aromatic molecules having a diatropic 14-electron cyclic π system. The UV–visible absorption spectra of compounds 12 and 13 exhibit extended cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to those of the related azulene derivatives having the same substituents. In addition, the first example of an aromatic substitution reaction of the methanocyclopentacycloundecene ring system has been studied, and shows that the compounds 12 and 13, like azulene, undergo trifluoroacetylation under exceptionally mild conditions and exhibit the same site-selectivity as does azulene. The electrochemical properties of compounds 12 and 13 as well as the related azulene derivatives are also analyzed and discussed on the basis of MNDO calculations.

  新型3-乙氧基羰基-2-乙氧基-和2-乙氧基-4,9-亚甲基环五环十一碳烯12和13是通过9-氯-1,6-亚甲基[11]annulen-8-one 8、10π- 2-氯代酮与2-乙氧基-3-(乙氧基羰基)丙-2-烯叉基-和2-乙氧基丙-2-烯叉基三苯基膦的电子乙烯系，分别为7a和7b。反应途径包括将正膦 7a,b 迈克尔型加成到酮 8 上，随后质子迁移再生正膦部分，该部分经历分子内 Wittig 反应，以及芳构化，消除 HCl。 1H NMR谱表明化合物12和13是具有双异性14电子环状π体系的芳香族分子。与具有相同取代基的相关甘菊环衍生物相比，化合物 12 和 13 的紫外-可见吸收光谱根据最长吸收最大值的红移表现出芳香族周长的扩展循环共轭。此外，还研究了亚甲基环五环十一碳烯环系的芳香族取代反应的第一个实例，结果表明化合物12和13与甘菊环一样，在极其温和的条件下进行三氟乙酰化，并表现出与甘菊环相同的位点选择性。基于MNDO计算，对化合物12和13以及相关甘菊环衍生物的电化学性质进行了分析和讨论。
• The Synthesis of Diethyl 2-Hydroxyazulene-1, 3-dicarboxylate from Troponoids and Some Reactions of 2-Hydroxyazulene Derivatives
  作者：Tetsuo Nozoe、Kahei Takase、Noboru Shimazaki

  DOI：10.1246/bcsj.37.1644

  日期：1964.11